Triplet Excited State of BODIPY Accessed by Charge Recombination and Its Application in Triplet-Triplet Annihilation Upconversion
Authors: Chen K., Yang W., Wang Z., Iagatti A., Bussotti L., Foggi P., Ji W., Zhao J., Di Donato M.
Autors Affiliation: State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, E-208 West Campus, 2 Ling-Gong Road, Dalian, 116024, China; LENS (European Laboratory for Non-Linear Spectroscopy), Via N. Carrara 1, Sesto Fiorentino, 50019, Italy; INO, Istituto Nazionale di Ottica Largo Enrico, Fermi 6, Florence, I-50125, Italy; Dipartimento di Chimica, Università di Perugia, via Elce di Sotto 8, Perugia, 06123, Italy; School of Chemistry, Dalian University of Technology, E-208 West Campus, 2 Ling-Gong Road, Dalian, 116024, China
Abstract: The triplet excited state properties of two BODIPY phenothiazine dyads (BDP-1 and BDP-2) with different lengths of linker and orientations of the components were studied. The triplet state formation of BODIPY chromophore was achieved via photoinduced electron transfer (PET) and charge recombination (CR). BDP-1 has a longer linker between the phenothiazine and the BODIPY chromophore than BDP-2. Moreover, the two chromophores in BDP-2 assume a more orthogonal geometry both at the ground and in the first excited state (87 degrees) than that of BDP-1 (34-40 degrees). The fluorescence of the BODIPY moiety was significantly quenched in the dyads. The charge separation (CS) and CR dynamics of the dyads were studied with femtosecond transient absorption spectroscopy (k(CS) = 2.2 X 10(11) s(-1) and 2 X 10(12) s(-1) for BDP-1 and BDP-2, respectively; k(CR) = 4.5 X 10(10) and 1.5 X 10(11) s(-1) for BDP-1 and BDP-2, respectively; in acetonitrile). Formation of the triplet excited state of the BODIPY moiety was observed for both dyads upon photoexcitation, and the triplet state quantum yield depends on both the linker length and the orientation of the chromophores. Triplet state quantum yields are 13.4 and 97.5% and lifetimes are 13 and 116 mu s for BDP-1 and BDP-2, respectively. The spin-orbit charge transfer (SO-CT) mechanism is proposed to be responsible for the efficient triplet state formation. The dyads were used for triplet-triplet annihilation (TTA) upconversion, showing an upconversion quantum yield up to 3.2%.
Journal/Review: JOURNAL OF PHYSICAL CHEMISTRY A
Volume: 121 (40) Pages from: 7550 to: 7564
More Information: We thank the NSFC (21473020, 21673031, 21273028, 21421005, and 21603021), Program for Changjiang Scholars and Innovative Research Team in University [IRT_13R06], and the Fundamental Research Funds for the Central Universities (DUT16TD25, DUT15ZD224, DUT2016TB12) for financial support.KeyWords: Absorption spectroscopy; Charge transfer; Chromophores; Insecticides; Quantum theory; Quantum yield, Charge recombinations; Charge separations; Excited-state properties; Femtosecond transient absorption spectroscopy; First excited state; Orthogonal geometry; Photo-induced electron transfer; Triplet-triplet annihilation, Excited statesDOI: 10.1021/acs.jpca.7b07623Citations: 35data from “WEB OF SCIENCE” (of Thomson Reuters) are update at: 2020-08-02References taken from IsiWeb of Knowledge: (subscribers only)Connecting to view paper tab on IsiWeb: Click hereConnecting to view citations from IsiWeb: Click here